Mineral oil composition



Patented Oct, 24, 1944 UNITED [STATES PATENT FFlCE MINERAL on.COMPOSITION Rush F. McClesry, Beacon, N. Y., assignor to The TexasCompany, New York, N. Y., a corporation of Delaware No Drawing.

17 Claims.

'I'his invention relates to an improved lubricating oil adapted for usein internal combustion engines and particularly to lubricating oilhaving one or more additive ingredient incorporated therein.

It is generally recognized that in the recent development of internalcombustion engines, and

' particularly engines designed for heavy duty service, the increase inoperating temperatures and engine speeds, together with the reduction ofclearances and the use of hard bearing alloys such as copper-lead,cadmium-silver, etc., has set up such severe operating conditions as tonecessitate improvement in the highly refined mineral oils refined foruse as lubricants. These rigorous operating conditions which are mostton temperatures range from approximately 425 F. to 650 F. and pressuresfrom'the oxidizing combustion gases areas high as 750 to 1150 pounds persquare inch, have seriously accentuated such problems of corrosion,oxidation and varnish and lacquer'formation in the refined minerallubricating oils with the resultant deleterious effect on the efliciencyof the'engines. The nature and extent of these problems depend upon theconditions of operation of the particular engine type and upon the type,and

- extent of refining of the base oil used, and numerous other factors.

The tendency of mineral lubricating oils to I deposit carbonaceousmaterials which are com-' monly referred to'as varnish and lacquerdeposits about the valves, rings, pistons, cylinders andother engineparts, can be largely overcome by the addition of certain types ofadditive ingredients which possess detergent qualities when dissolved ordispersed in lubricating oils. By detergent properties is meant not onlythat property which aids in dispersing, removing or purging foreignmaterials which accumulate on the surface of the engine parts, but alsothat property which prevents the accumulation or deposition of suchmaterials, as distinguished from solvent action upon the accumulationsor deposits.

It is the object of the present invention to provide a mineral oilcomposition which pos-' Application November 7. 1941, 8611.81 N0-418,161

1 alcohol radical may be retained as such or in prevalent in diesel andgasoline engines used in i heavy duty bus and tractor service where thepisthe form of its corresponding metal alcoholates.

When describing the compounds of the present invention throughout thespecification and claims, it is to be understood that-when reference ismade toan ether linkage or an alcohol or an alcoholate radical, thecorresponding thio ethers, thio alcohols and thio alcoholates are meantto be included. This class of compounds maybe illustrated by thefollowing structural formula I R p-Ce- (XRiY) s in which C is acycloaliph atic nucleus; R may be a hydrogen, alkyl, aryl, aralkyl,'cycloalkyl or n'aphthenyl radical together with substituted derivatives thereof R1 is an aliphatic radical which may contain oxygen orsulfur substituents or both in the form of ether and thio ether linkagestogether with further substituents in the,

form of halogen, oxygen, sulfur or nitrogen derivatives; X may beeitheroxygen or sulfur; Y may be an hydroxyl radical (OH), 9, sulfhydrylradical (SH) or metal salts thereof; and y and z are integers of one ormore. The cycloaliphatic nucleus designated by C in the formula includescycloaliphatlc radicals containing one or more cyclic nuclei togetherwith hydrogenated aromatic radicalspossessing varying degrees-ofhydrogenation. The monocyclic nuclei may be derived from suchcycloaliphatic compounds as cyclopentane, cyclohexane, cyclcheptane,cyclooctane etc.- together with their substituted derivatives. Thpolycyclic nuclei may be derived' from such compounds as bicycle-hexane,bicyclooctane, decahydronaphthalene and the compounds obtainedirompetroleum oil, usually rerange of 0.1 and 5.0 per centby weightdepending upon the particular base oil used and the type of engine andservice involved. However, the range of proportions between 0.25 and 2.0per cent by weight has been foundto be particularly eflective inimparting excellent detergent properties to the mineral lubricating oil.

In illustrating the methods of preparing the aforementioned class ofcompounds and the resultant effect of these compounds when incorporatedin a mineral lubricating oil, one compound-namely, calcium diamylcyclohexoxy ethylate-is presented as being representative of the generalclass of additives. It isto be understood that the method of preparingthese compounds, which is illustrated in the subsequent example, ismerely one or the numerous classical methods of synthesis which may beused.

EXAMPLE I which cpnsisted of diamyl cyclohexoxy ethanol weighed 440grams and had a hydroxyl number of 189.

ExmI-n II 400 grams of diamyl cyclohexoxy, ethanol prepared inaccordance with Example I was added- .to a solution of 40.0 grams ofcalcium dissolved in 1000 cc. of liquid ammonia with substantialagitation. Two liters of toluene were added and the ammoniaevaporatedofi. The toluene solution of calcium diamyl cyclohexoxyethylate was warmed and filtered. The toluene was removed bydistillation in vacuo and the calcium salt dissolved in an equal weightof lubricating oil to give a 50% concentrate. a

It is to be understood that in place or the dian yl cyclohexanol used inExample 1, other substituted or unsubstituted cycloaliphatic compoundsmay be used and that in place of the alcohol, other aliphatic alcoholsor mercaptans may be used. Further, the calcium ofExample 11 may besubstituted by any of the other metals previously mentioned.

As a test to indicate the effectiveness of. the

compounded oils proposed by the present invention under actual operatingconditions, a special test was devised which is a modification of thetest described in Diesel Lubricant Test Manual, Laboratory Test No. 1,issued by the Caterpillar Tractor Company. This test was carried out ina single cylinder Diesel engine operating at 900 R. P. M. with a waterjacket temperature of 175 F. and run continuously for periods of 120 and240 hours or until rings are stuck as indicated by the increase inblow-by. The crankcase oil was drained every sixty hours and fresh oiladded. thereto. At the end of each test period, the engine wasthoroughly examined and any carbonaceous deposits. lacquer and sludgeformation, etc. were noted and the principal engine parts classifiedaccording to their condition. In the present instance the reference oilwas a mixed base 501- Heat groove v Filter containing 0.5%

ventrefined, dewaxed Mid-Continent lubricating oil of an SAE 30 grade.The results of the test runs on the reference oil and the reference oilethylate are as follows:

R'efeqence oil Engine part 120 hours 240 hours Normal Normal.

B B. m t i" ng grooves Piston skirt O 0. Under piston deposit B. FilterA B. Ring lands.. A B. Rings stuck None. One. Ring cleanliness #1, 2clean; 3, 4 #l, 2, ll, clean;

lacquer; #5, 6 #4, 5, 0 black slight sludge. lacquer. Bearing weightloss (grams).. 7 0.027.

Reference oil plus 0.5% calcium diamyl cyclohezozuethylate Engine part120 hours 240 hours Piston crown Normal grams Engine part RatingCondition noted No sending to very flue scufllng.

Up to 50% scuilod.

Up to scuifcd.

Open to 10% plugged.

Up to 50% plugged.

Up to 75% logged.

Over 75% p ugged.

Clean to heavy lacquer.

Slight carbon ilti N c. l and 2 grooves Scuillng above host groove.

.Ring groove Heavier deposi Clean to very Trace varnish to lightvarnish. Heav varnish to lacquer.

Very oav varnish. Clean to d scoloration. Trace deposit. Heavy deposit.Clean to mesh pattern visible. Mesh pattern visible to slight amount mudsludge. Heavy .mud or carbonaceous de- 8 t of? to heavy varnish. Heavyvarnish to carbon deposit.

Piston skirt...

Under piston dcposit'..

Obviously many modifications and variations oiv the invention. ashereinbefore set forth, may be made without departing from the spiritand scope thereof, and therefore only such limitations should be imposedas are indicated in the appended claims.

I claim: l l. A lubricant consisting essentially of a minerallubricating oil and having incorporated therein a small proportion,sufficient to impart antioxidant properties to said lubricating oil, ofan oil-soluble. compound selected from the group consisting ofcycloaliphatic-aliphatic ether-alcohols and their corresponding metalalcoholates. 2. A lubricant as claimed in claim 1 in which Ring land";

the cycloaliphatic constituent contains a cyclocalcium .diamylcyclohexoxy slight trace of varnish weight of an oil-soluble compound ofthe following general formula Rv-C- (mm s alkyl, aryl, arallgvl,cycloalkyl and naphthenyl radicals, R1 is an aliphatic radical, X is anele-- ment from the group consisting of oxygen and sulfur, Y is aradical selected from the group consisting of hydroxyl and sulfhydrylradicals and metal salts thereof, and y and z are integers of at leastone.

4. An improved lubricant as claimed in claim 3 in which Y is a metaloxide.

5. A lubricant consisting essentially of a mineral lubricating oil andhaving incorporated therein 0.1 to 5.0% by weight of an oil-solubleaikylated cyclohexyl-aliphatic ether-alcoholate.

6. An improved lubricant comprising a mineral lubricating oil containing0.1 to 5.0 per.cent by weight of an oil soluble compound of thefollowing general'formula in which is a cycloaliphatic radical, R isaradical from the group consisting of a hydrogen, alkyl, aryl, aralkyl,cycloalkyl and naphthenyl radicals,

R1 is an aliphatic radical, X is an element from the group consisting ofoxygen and sulfur, Y is a radical selected from the group consisting ofhydroxyl and sulfhydryl radicals andmetal salts thereof. and y and z areintegers of at least one.

7. An improved lubricating oil adapted for use .-in internal combustionengines comprising a mineral lubricating oil having incorporated,

,. sisting of hydroxyl and sulfhydryl radicals and metal salts thereof,11 and z are integers of at least one and n is a numeral selected fromthe group consisting of 0, 1, 2, 3, 4 and 5.

' 8. An improved lubricating oil as claimed in claim 7 in which Y is ametal oxide.

9. An improved lubricant comprising a mineral lubricating oil containing0.25 to 2.0 per cent by weight'of a compound of the following in which 0is a cycloaliphatic radical, R is a radical selected from the groupconsisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, and naphthenyl radicals, Re is an aliphatic radical contalningfr'om 1 to carbonatoms,x is an element selected from the group consisting of oxygen andsulfur, Y is a radical selected from the group consisting of hydroxyland sulfhydryl radicals and metal salts thereof, 11 and,z are integersof at least one and n is a numeral selected from the group consisting0H), 1, 2, 3, 4 and 5.

10.A mineral oil composition. comprising a mineral lubricating oilcontaining 0.1 to 5.0% by weight of an oil-soluble alkaline earth metalsalt of a cycloaliphatic-aliphatic ether-alcohol.

11. An lubricant a minweight of a compound of the following generallected from the group consisting of oxygen and eral lubricating oilcontaining 0.1 to 5.0% In weight of an oil-soluble compound of thefollowing general formula:

Ry-C-[X-(RiXln-Rfll;

in which 0 is a cycloaliphatic radical, R is an alkyl radical, R: is ahydrocarbon radical containing up to 5 carbon atoms, X is an elementselected from the group consisting of oxygen and sulfur, Y is a radicalselected from. the group consisting of hydroxyl and sulfhydryl radicalsand metal salts thereof, 11 and z are integers of at least one, and n isa numeral selected from the group consisting of 0, 1, 2, 3, 4 and 5.

12. An improved lubricant comprising a min eral lubricating oilcontaining 0.1 to 5.0% by weight of an oil-soluble compound of thefollowing general formula:

in which 0 is a cyclohexyl radical, R is an alkyl radical, R: is analiphatic radical containing two carbon atoms, X is oxygen, Y is analkaline earth metal oxide, 9 is an integer of at least one, s is one,and n is 0.

13. An improved lubricating 011 comprising a mineral lubricating oilcontaining 0.1, to 5.0% by formula:

n o-ix-(mxn-mrh in which 0 is a cycloaliphatic radical, R is a radicalselected from the group consisting of hydrogen, alkyl, aryl, aralkyl,cycloalkyl, and naphthenyl radicals, R: is an aliphatic radicalcontaining two carbon atoms, x is an element assulfur,.Y is a radicalselected from the group consisting of hydroxyl and sulfhydryl radicalsand metal salts thereof, :1 and z are integers of at least one,andnis 0.v

v 14. A lubricant comprising a major proportion of a mineral lubricatingoil and 0.1 to 5.0% by weight of an oil-soluble compound of thefollowinggenerel formula a in which 0 is acycloaliphatic radical, R itsrad sulfur, Y is a metal sulfide radical, and y and s are integers of atleast one. 15. An improved lubricating oil adapted for use-in internalcombustion engines comprising a mineral, lubricating .o i1 havingincorporated therein 0.1 to 5.0%. by weight of a compound of m thefollowing general formula Rr-C["X+-(Rax)nlhYlin which G is acycloaliphatic radical, R is a radical-selected from the groupconsisting of lwdrm" gen, alkyl. aryl, aralkyl, cycloalkyL-andnaphthenyl radicals, R: is an aliphatic radical containingfrom 1 to 5carbon atoms, at is an element selected from the group consisting ofmg'en and sulfur, Y is a metal sulfide radicaLy ing oil havingincorporated therein an amount,

less than 5% by weight, butsuiiicient to impart anti-oxidant to saidoihof an oil-soluble compound selected irom the group consisting' 01'cycloaliphatic-aliphatic ether-alcohols and their corresponding metalalcoholetes;

17. A lubricant comprising a; minerel .lubrieating oil havingincorporated therein a small amount; less than 5% by weight, butsufllcient to impart anti-oxidant properties to said .oil, of

an oil-soluble compound of the following general formula m-c- (mm 2 inwhich c is s cycloaliphetic radical, R is a M- ical from the. groupconsisting of a hydrogen, alkyl, aryl, arelkyl, cycloalkyl andnaphthenyl radicals, R1 is an aliphaticradical, X is an elemeat fromthe-group consisting of oxygen and sulfur, Y is a, radical selected fromthe group consisting of hydroxyl and sulfhydryl radicals and the metalsalts thereof, and y and 2 are intesers of at least one.

- RUSH F. McCLEARY.

